Construction and Building Materials 157 (2017) 829–838

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Thermal and mechanical properties of high-performance fiber-

reinforced cementitious composites after exposure to high temperatures
Xiuling Li a,b, Yi Bao b,⇑, Lele Wu a, Qingxi Yan a, Hongyan Ma b, Genda Chen b, Huining Zhang c
a
School of Civil Engineering, Shandong Jianzhu University, Jinan, Shandong 250101, China
b
Department of Civil, Architectural and Environmental Engineering, Missouri University of Science and Technology, Rolla, MO 65409, USA
c
School of Engineering & IT, University of Melbourne, Melbourne, Victoria 3010, Australia

h i g h l i g h t s

 Thermal properties of HPFRCCs after exposure to high temperatures.

 Mechanical properties of HPFRCCs after exposure to high temperatures.
 Effects of mix proportions on thermal properties of HPFRCCs.
 Effects of mix proportions on mechanical properties of HPFRCCs.

a r t i c l e i n f o a b s t r a c t

Article history: This paper investigates residual thermal and mechanical properties of high-performance fiber-reinforced
Received 27 May 2016 cementitious composites (HPFRCCs) proportioned with high-volume fly ash after exposure to 200, 400,
Received in revised form 3 July 2017 600, and 800 °C. The investigated thermal and mechanical properties include the thermal conductivity,
Accepted 21 September 2017
specific heat, compressive strength, tensile strength, tensile ductility, and density. The effects of five
mix proportioning variables on the material properties are evaluated, which include the water-to-
binder ratio (0.24–0.36 by mass), sand-to-binder ratio (0.36–0.66 by mass), fly ash content (60%–75%
Keywords:
by mass), polyvinyl alcohol fiber content (1.5%–2.2% by volume), and superplasticizer content
High-performance fiber-reinforced
cementitious composites (HPFRCCs)
(0.10%–0.15% by mass). Experimental results reveal significant dependence of the residual thermal and
High temperature mechanical properties on temperature and the mix proportion, which can be attributed to a series of
Thermal properties chemical and physical reactions that occur at elevated temperatures. This study can facilitate optimiza-
Mechanical properties tion of mix proportions of HPFRCCs for enhanced thermal and mechanical performance in fire or high
Mix proportions temperature applications.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Background and objectives
Besides the load bearing functions, concrete serves as thermal
and chemical barriers that insulate steel from fire impingement
and exposure to corrosive matters, thus substantially delaying
the degradation of reinforced concrete structures [1,2]. In addition,
concrete has better heat preservation performance than steel, due
to the low thermal conductivity of concrete, which is beneficial for
the development of sustainable buildings with low energy con-
sumption [3]. However, conventional concretes are brittle and
prone to cracking. Once cracked, the barrier effects are significantly
⇑ Corresponding author.
E-mail address: ybc86@mst.edu (Y. Bao).
reduced, compromising the durability and fire resistance of rein-
forcement concrete structures [4].
High-performance fiber-reinforced cementitious composites
(HPFRCCs) have been developed to provide high cracking resis-
tance and durability. Ultra-high-performance concrete (UHPC)
was developed with a low water-to-binder ratio (w/b < 0.25 by
mass) and superior mechanical strength and durability [5–7].
Recently, eco-friendly UHPCs have been proposed, which are pro-
portioned with high-volume supplementary cementitious materi-
als such as fly ash and ground granulated blast slag [8–12], and
implemented to fabricate structural elements [13–16]. However,
some researchers reported that the low permeability of cementi-
tious matrix could lead to explosive spalling at elevated tempera-
tures, due to buildup of vapor pressure, which can be attributed to
the vaporization of water and a series of physicochemical reactions

https://doi.org/10.1016/j.conbuildmat.2017.09.125
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
830 X. Li et al. / Construction and Building Materials 157 (2017) 829–838
of concrete [17]. In the meanwhile, engineered cementitious com-
posites (ECCs) have been developed to provide high tensile ductil-
ity by incorporating polymer fibers as reinforcement, such as
polyvinyl alcohol (PVA) fibers [18]. At normal temperature, the
fibers can bridge and restrain cracks, thus enhancing the tension
resistance [19]. At elevated temperatures, the fibers melt and/or
decompose, creating channels to relieve vapor pressure, which
benefits preventing the occurrence of explosive spalling [20–27].
Recently, eco-friendly HPFRCCs have been developed with the
use of high-volume supplementary cementitious materials, and
implemented to repair civil structures [28–30]. The HPFRCCs have
shown superior mechanical properties, and are promising for fire-
resistant or other high temperature applications.
In structural fire engineering, the fire resistance or load-
carrying capacity of structures during and after fire hazards are
evaluated through thermo-mechanical analyses [31–33]. In a typi-
cal thermo-mechanical coupled analysis of a structure subjected to
elevated temperatures, detailed temperature distributions in the
structure are predicted based on the thermal properties [33]; then,
mechanical properties of materials, which are generally dependent
on temperature, are applied according to the predicted tempera-
ture distributions to evaluate the mechanical behaviors of the
structure. The mechanical properties of ECCs after exposure to high
temperature have been investigated in the literature [20–27]. The
residual compressive strength, stress-strain curves, and stiffness
of an ECC mixture after exposure to high temperatures up to
800 °C were studied [20]. The mechanical properties did not signif-
icantly change at temperatures up to 400 °C, and decreased as the
exposure temperature was further increased. The effects of fly ash
contents (55% and 70% by mass) and PVA fibers (0 and 2% by vol-
ume) on the residual mechanical properties of ECC were studied
[21]. The inclusions of fly ash and PVA fibers improved the fire
resistance of the ECC mixture. Coupled strain rate and temperature
effects on tensile properties of a mixture were investigated at tem-
peratures up to 150 °C [22]. Increasing the specimen size was
found to decrease the residual mechanical properties of ECC after
exposure to temperatures up to 800 °C [23]. After exposure to tem-
perature at 200 °C, an ECC mixture with 2% PVA fibers lost its ten-
sile strain-hardening behavior but the tensile strength did not
change significantly [24]; the ECC became brittle after exposure
to 300 °C. Water cooling was reported to partially recover the
residual mechanical properties of an ECC mixture after exposure
to temperatures up to 800 °C [25,26]. The residual tensile strength
and crack pattern were investigated for an ECC mixture after expo-
sure to temperatures up to 200 °C [27]. So far, the effects of mix
proportioning variables, such as the w/b, sand-to-binder ratio (s/
b), and fiber content, on the material properties of ECC after expo-
sure to high temperature have not been presented in detail. On the
other hand, the thermal conductivity of ECC before exposure to
high temperature, rather than during or after the exposure, was
studied [34]. Very limited investigations have been available on
the thermal properties of ECC after exposure to elevated tempera-
tures, which are essential for the evaluation of fire resistance of
ECC structures [31].
This research aims to investigate the thermal and mechanical
properties of HPFRCCs before and after exposure to elevated tem-
peratures (200, 400, 600, and 800 °C). The investigated properties
include the thermal conductivity, specific heat, compressive
strength, tensile strength, ductility, and density. Particular
emphases are placed on evaluating the residual thermal and
mechanical properties after exposure to elevated temperatures.
The effects of the w/b, s/b, fly ash content, PVA fiber content, and
superplasticizer content on the thermal and mechanical properties
are investigated. This study is a part of a systematical research on
development and evaluation of HPFRCC buildings subjected to
seismic and/or fire hazards.
2. Physicochemical reactions of concrete at normal and
elevated temperatures
The thermal and mechanical properties of concrete depend on
the microstructure, which forms as a result of a series of chemical
and physical reactions. In the presence of water, cement particles
hydrate and produce calcium silicate hydrate (C-S-H) gels, calcium
hydroxide (CH), AFt/AFm phases, and small amounts of other
hydrates [35]. With the growth of the hydrates, voids or pores
are partially filled. The hydration products are bound together
and form an integrated part that gradually hardens and possesses
mechanical strengths. The reduction in porosity and development
of binding force provide the basis for growth of mechanical
strengths. When pozzolanic materials are incorporated, reactive
silica in pozzolanic materials can react with CH, forming secondary
C-S-H, namely pozzolanic reaction. Pozzolanic reaction benefits
reducing the porosity and enhancing the durability of cement
based materials.
As temperature increases, a series of vaporization, dehydration,
dehydroxylation, and decomposition reactions occur, altering the
microstructure of the hardened matrix of concrete [17–25]. At
30–105 °C, evaporable water and a part of the bound water vapor-
izes; at 110–170 °C, gypsum and AFt/AFm phases decompose; at
180–300 °C, a part of C-S-H dehydrates; at 450–550 °C, dehydrox-
ylation of CH undergoes; at 700–900 °C, calcium carbonate decom-
poses. In the presence of PVA fibers, thermal pyrolysis of PVA fibers
starts at about 180 °C and accelerates at about 250 °C [36,37]. The
dehydration and decomposition reactions increase the total poros-
ity and the average pore diameter and deteriorate the binding
effect, thus, resulting in reduction in mechanical strengths and
stiffness. In the case of fast heating scenarios or concretes with
low permeability, the existence of thermal gradient and the
buildup of vapor pressure can cause increased internal stresses,
resulting in cracking and/or explosive spalling. With adequate
use of PVA fibers that provide percolated pathway to relieve vapor
pressure, spalling can be prevented.
3. Experimental program
3.1. Raw materials and mixing procedure
The mixtures were proportioned with ASTM Type I ordinary
Portland cement (OPC), Class F fly ash (FA), finely ground quartz
sand, PVA fibers, and water. The chemical composition and physi-
cal properties of the cement and the fly ash are listed in Table 1.
The quartz sand has a mean particle size (d50) of 115 lm, a density
of 2.63 g/cm3, and a SiO2 content of 98.9%. The material properties
of the PVA fibers are listed in Table 2. Thermal pyrolysis of the PVA
fibers occurs rapidly above 250 °C [36,37]. A polycarboxylic acid
superplasticizer (SP) was incorporated to enhance the flowability
of mixtures [38].
The mixtures were mixed using a 19-L mortar mixer. The
cement, fly ash, and quartz sand were first mixed in dry condition
Table 1
Chemical composition and physical properties of cement and fly ash.
OPC FA
SiO2 (%) 18.9 46.9
Al2O3 (%) 4.9 28.5
Fe2O3 (%) 3.6 6.2
CaO (%) 64.1 2.3
MgO (%) 0.8 1.2
SO3 (%) 1.7 0.9
Loss of ignition (%) 3.2 2.8
Specific surface area (m2/kg) 350 460
Specific gravity (g/cm3) 3.15 2.38
 X. Li et al. / Construction and Building Materials 157 (2017) 829–838 831

Table 2 temperature in air for testing. For each mixture, the specimens
Material properties of the PVA fibers. were divided into five groups: one group of specimens were tested
Properties Values at room temperature immediately after oven drying; the other four
Length (mm) 12.0 groups of specimens were respectively heated in a computer-
Diameter (mm) 0.04 controlled, electrically heated furnace (chamber dimensions:
Density (g/cm3) 1.31 300  500  200 mm), at a heating rate of 5 °C/min until reaching
Tensile strength (GPa) 1.62 target temperatures (200, 400, 600, and 800 °C). Once reached, the
Elastic modulus (GPa) 42.8
Poisson’s ratio 0.42
target temperatures were sustained for 2 h to achieve thermal
Ultimate elongation (%) 6–8 steady state in the specimens, and then cooled to room tempera-
Specific heat (J/gK) 1.68 ture in air for testing. During the heating operation, explosive spal-
Melting point (°C) 225 ling did not occur. The specimens were kept in sealed plastic bags
immediately after taken from the oven, in order to prevent ingress
of moisture. For each test, three specimens were tested, and their
at 60 rpm for 2 min. The superplasticizer was dissolved in water, average results are reported.
and then added into the mixer and mixed at 120 rpm for 8 min.
Finally, the PVA fibers were gradually added within 2 min, fol- 3.4. Scanning electron microscopy
lowed by mixing for 2 min.
The microstructures of specimens after heat treatment were
3.2. Mix designs examined using a Hitachi S-4700 scanning electron microscope
(SEM). Pieces from fractured specimens were taken as samples. A
The effects of five mix proportioning variables on material prop- thin gold layer was coated on the surface of each sample before
erties were evaluated using 16 mixtures designed with an orthog- it was put in the microscope. SEM images were taken at 30
onal method [39]. Table 3 lists the investigated mixtures in a magnification.
L16(45) table, including five variables at four levels. The five vari-
ables are the w/b at 0.24, 0.28, 0.32, and 0.36 by mass, the s/b at 3.5. Mass loss test
0.36, 0.46, 0.56, and 0.66 by mass, the fly ash (FA) content at
60%, 65%, 70%, and 75% by mass, the PVA fiber content at 1.5%, The mass loss of specimen is used as an index to evaluate the
1.7%, 2.0%, and 2.2% by volume, and the superplasticizer (SP) con- effect of high temperature exposure. For this purpose, the mass
tent at 0.10%, 0.15%, 0.20%, and 0.25% by mass. Each variable is con- of each specimen was measured using a laboratory balance scale
sidered independent, and interactions between different variables before and after exposure to elevated temperatures. The weighing
are not considered. The investigated levels of each variable are uni- capacity and readability are 2.2 kg and 10 mg, respectively.
formly distributed in the L16(45) table. Each level corresponds to
four mixtures, of which the average result is calculated to repre- 3.6. Thermal property tests
sent the corresponding level. For instance, the average result of
the mixtures M1 to M4 in Table 3 represents the result correspond- Thermal properties of specimens were evaluated before and
ing to the w/b at 0.24. The flowability of mixtures was evaluated by after exposure to high temperatures using a Thermal Property Ana-
slump flow in accordance with GB/T 2419-2005 [40]. lyzer (Hot Disk TPS 2500S) and Kapton sensors, as shown in Fig. 1
(a)–(c). The measurement ranges of thermal conductivity and
3.3. Curing and heating of specimens specific heat are 0.005–1800 W/mK and up to 5 MJ/m3K, respec-
tively. The measurement reproducibility and accuracy were within
All specimens were covered with wet burlap and plastic sheet 1% and 5%, respectively. During the measurement, the sensor tem-
immediately after casting. They were stored at room temperature perature is increased through electric effects, and heat dissipates
(22 ± 2 °C) for 24 h, and then demolded and cured in an environ- into the sample on both sides of the sensor at a rate depending
mental chamber at room temperature and a relative humidity of on the thermal properties of the specimen. The thermal properties
95 ± 5% until the age of 28 days. Then, the specimens were dried are determined by analyzing the sensor’s temperature history. The
in an oven at 100 °C for 24 h and naturally cooled to room surface roughness of the specimen plays an important role in
ensuring accurate measurement results, so before thermal tests,
the surfaces of the specimens were polished using a sand paper,
Table 3 as shown in Fig. 1(b).
Mix proportions.

Mixture w/b s/b FA content (%) Fiber content (%) SP content (%) 3.7. Mechanical property tests
M1 0.24 0.36 60 1.5 0.10
M2 0.24 0.46 65 1.7 0.15 The compressive strengths of the mixtures were evaluated
M3 0.24 0.56 70 2.0 0.20
using 70.7 mm standard cube specimens in accordance with JGJ/
M4 0.24 0.66 75 2.2 0.25
M5 0.28 0.36 70 1.7 0.25 T70-2009 [41]. The specimens were tested using a load frame (load
M6 0.28 0.46 75 1.5 0.20 capacity: 100 kN) at a rate of 500 N/s. The tensile behaviors were
M7 0.28 0.56 60 2.2 0.15 tested using dog-bone specimens with a cross section of
M8 0.28 0.66 65 2.0 0.10 30  15 mm, as depicted in Fig. 2(a). The specimens were tested
M9 0.32 0.36 75 2.0 0.15
M10 0.32 0.46 70 2.2 0.10
using a low capacity load frame at a rate of 0.15 mm/min. The load
M11 0.32 0.56 65 1.5 0.25 and elongation were respectively measured using a 10 kN load cell
M12 0.32 0.66 60 1.7 0.20 embedded in the load frame and a clip-on gauge. The measuring
M13 0.36 0.36 65 2.2 0.20 range of the clip-on gauge is ±12.5 mm. Fig. 2(b) plots the stress-
M14 0.36 0.46 60 2.0 0.25
strain curves for the mixtures M10 and M11. The tensile strength
M15 0.36 0.56 75 1.7 0.10
M16 0.36 0.66 70 1.5 0.15 and ductility are defined as the peak tensile stress and ultimate
strain, respectively.
832 X. Li et al. / Construction and Building Materials 157 (2017) 829–838

Fig. 1. Photographs of the instrument and specimen for evaluation of thermal properties: (a) the Hot Disk instrument; (b) a specimen polished using sand paper; (c)
measurement operation.

Tensile stress (MPa)

4

1 M11 M10
0
0 1 2 3 4
Strain (%)
(a) ( b)
Fig. 2. Tensile test: (a) setup and specimen (unit: mm); (b) tensile stress-strain curves at 22 °C.

4. Experimental results and discussions
4.1. Density
After exposure to elevated temperatures, the volumes of speci-
mens slightly shrink due to water loss. However, since the volume
shrinkage is relatively small compared with the mass loss, the vol-
ume change is negligible for the evaluation of density change. The
density results (average ± standard variation at 95% confident
level) of all mixtures are summarized in Fig. 3. The density
decreases with temperature, likely due to water loss, dehydration,
dehydroxylation, and decomposition of hydration products of the
cementitious materials, and thermal pyrolysis of PVA fibers [37].
As the maximum heating temperature is increased up to 800 °C,
2
1.9
Density (g/cm3)
the average bulk density of the investigated mixtures is reduced
by 13%.
The effects of mix proportions on the density of mixtures are
shown in Fig. 4. As the w/b is increased from 0.24 to 0.36, the den-
sity is reduced by 3% at 22 °C and 9% at 800 °C, which can be attrib-
uted to the porosity that increases with the w/b. As the s/b is
increased from 0.36 to 0.66, the density is increased by 5% at
22 °C and 7% at 800 °C, due to the fact that the quartz sand is den-
ser and more stable than the cement hydrates. The density
decreases with the fiber content, likely due to the fact that more
air may be introduced to the mixture during mixing when more
PVA fibers are added. The density reduction at high temperature
can be partially attributed to the low thermal stability of the PVA
fibers. However, since the fiber content was low, the reduction
due to the fiber content was less than 3%. The FA and the SP con-
tents do not demonstrate significant effect on the density.
4.2. Thermal conductivity
The thermal conductivities (average ± standard variation at 95%

1.8 confident level) vs. the heating temperature are plotted in Fig. 5(a).
As the heating temperature is increased from 22 to 800 °C, the
1.7 average thermal conductivity is reduced by 42%. The temperature
dependence of the average thermal conductivities can be linearly
1.6 fitted, with a coefficient of determination of 0.99, indicating a good
correlation. The thermal conductivities of the test specimens can
1.5 also be correlated with the density, as plotted in Fig. 5(b). Overall,
0 200 400 600 800 the thermal conductivity increases with density at a rate of
2.21 W
cm3/gmK.
Temperature (°C)
Fig. 6 shows the thermal conductivity associated with mix pro-
Fig. 3. Density vs. the highest heating temperature (T). Each error bar represents ±r portions. As the w/b is increased from 0.24 to 0.36, the thermal
(standard deviation) at 95% confident level. conductivity does not change significantly at 22 °C, but it decreases
 X. Li et al. / Construction and Building Materials 157 (2017) 829–838 833

Fig. 4. Density vs. mix proportions.

1.6 1.6

Thermal conductivity
Thermal conductivity

1.4 k = -7.41×10-4T + 1.35 1.4

R² = 0.99

(W/mK)
(W/mK)

1.2 1.2

1 1
k = 2.21 - 2.77
0.8 0.8 R² = 0.92

0.6 0.6
0 200 400 600 800 1.5 1.6 1.7 1.8 1.9 2
(a) Temperature (°C) (b) Density (g/cm3)

Fig. 5. (a) Thermal conductivity (k) vs. the highest heating temperature, error bars at 95% confident level. (b) Thermal conductivity vs. density (q).

Fig. 6. Thermal conductivity vs. mix proportions.

with the w/b at 200–800 °C. At 800 °C, as the w/b is increased from
0.24 to 0.36, the thermal conductivity is reduced by 15%. As the s/b
is increased from 0.36 to 0.66, the thermal conductivity is
increased by 16% at 22 °C and 18% at 800 °C. As the FA content is
increased from 60% to 75%, the thermal conductivity is reduced
by 7% at 22 °C and 6% at 800 °C. As the PVA fiber content is
increased from 1.5% to 2.3%, the thermal conductivity is reduced
by 7% at 22 °C and 16% at 800 °C. As the SP content is increased
from 0.1% to 0.25%, the thermal conductivity is increased by 3%
at 22 °C and 5% at 800 °C.
Solid state physics related to the thermal conductivity is
reviewed to understand the experimental results. The primary heat
transfer mode in solids is thermal conduction that occurs as free
electrons or neighboring atoms or molecules interact and exchange
energies with each other [42]. Internal energy in solids can be
transferred by vibrations and collisions of molecules or atoms,
propagation and collisions of phonons, and diffusion and collisions
of free electrons. In non-metal materials such as HPFRCCs that are
poor in free electrons, the thermal conductivity is primarily rely on
the lattice vibrations (phonons), and the thermal conductivity is
proportional to the mean free path of phonon, which represents
the average distance between two consecutive collisions [42]. In
the presence of defects, boundaries, or other phonons, phonon
scatterings take place and shorten the mean free path of phonon,
thus reducing the thermal conductivity [43]. The defects include
crystal defects, impurities, and discontinuities such as voids and
cracks.
With increases in temperature, the porosity of specimen is
increased [17] and the connectivity between solid particles is dete-
riorated, which means more defects and boundaries are created,
thus, reducing the thermal conductivity. Overall, increasing the
w/b and the fiber content tends to increase the porosity, and,
hence, reducing the thermal conductivity. The increase in s/b leads
to higher thermal conductivities, which can be attributed to the
834 X. Li et al. / Construction and Building Materials 157 (2017) 829–838
2 2
1.9
Specific heat (MJ/m3K)
1.8
1.7
1.6
1.5
1.4
0 200 400
(a) Temperature (°C)
Fig. 7. (a) Specific heat (c) vs. the heating temperature, error bars at 95% confident level. (b) Specific heat vs. density.
relatively high thermal conductivity of quartz sand, due to its high
crystallinity, thermal stability, and less defects [43]. The slight
increases in thermal conductivity owing to the SP content are
likely due to the enhanced homogeneity of mixtures. As the fly
ash content is increased from 60% to 75%, the thermal conductivity
slightly deceases; however, the change is not significant.
The reduction in thermal conductivity implies more thermal
insulation. Although a reduced thermal conductivity tends to
increase thermal gradient, resulting in internal stresses and
increases the risk of spalling, the incorporation of PVA fibers can
partially or completely compensate the thermal gradient effect
by relieving the vapor pressure.
4.3. Specific heat
Significant reduction in the volumetric specific heat of the mix-
tures after exposure to elevated temperatures is revealed in Fig. 7
(a). As the heating temperature is increased from 22 to 800 °C, the
average thermal conductivity of the mixtures is reduced by about
20%. Such reduction may be attributable to the migration of water
molecules and hydroxyl groups at elevated temperatures, which
reduces the hydrogen bonds in the mixtures. Thus, the specific heat
is reduced after high temperature treatment [44]. Moreover, the
dehydration, hydroxylation, and decomposition reactions increase
the porosity and reduce the density, making the specimens become
easier to warm up with the same heat energy input [45]. From 22
to 200 °C, reduction in hydrogen bonds and increase in porosity
can be attributed to vaporization of free water, decomposition of
AFt/AFm, and dehydration of a part of C-S-H. From 200 to 400 °C,
the loss of PVA fibers increases the porosity of specimens. From
400 to 600 °C, dehydroxylation of CH tends to reduce hydrogen
bonds and increase the porosity. From 600 to 800 °C, decomposi-
tion of limestone leads to further reduction in specific heat.
1.9
Specific heat (MJ/m3K)
1.8
1.7
1.6 c = 1.31 - 0.57
R² = 0.84
1.5
1.4
600 800 1.5 1.6 1.7 1.8 1.9 2
(b) Density (g/cm3)
Besides, as temperature is increased up to 800 °C, dehydration of
C-S-H and release of non-evaporable water lead to reduction in
hydrogen bonds and increases in porosity, reducing the specific
heat. Since the specific heat is related to the loss of water and
the dehydration, hydroxylation, and decomposition reactions, it
can be related to the density, as plotted in Fig. 7(b). The data can
be regressed using a linear equation with a coefficient of determi-
nation of 0.84.
Fig. 8 shows the results of specific heat associated with mix pro-
portions. There are two competing effects of the w/b. On one hand,
increasing the w/b tends to increase the porosity, reducing the heat
capacity. On the other hand, particularly for mixtures with low
w/b, increasing the w/b tends to increase the degree of hydration
[44], producing more hydrates that contains more bound water,
increasing the heat capacity [45]. The combination of these two
mechanisms leads to a maximum specific heat at a particular
w/b. As shown in Fig. 10, increasing the w/b from 0.24 to 0.28
increases the specific heat. However, increasing the w/b from
0.32 to 0.36 reduces the specific heat. A w/b in the range of
0.28–0.32 gives the highest specific heat. As for the s/b increasing
from 0.36 to 0.66, the specific heat is reduced by 4% at 22 °C; how-
ever, it is increased by 8% at 800 °C, demonstrating an opposite
trend. At normal temperature, increasing s/b leads to a reduction
in water content and the amount of hydrates, thus, reducing the
specific heat. However, at high temperatures, the relatively high
thermal stability of quartz sand helps retain the specific heat. Thus,
increasing the s/b results in a higher specific heat. As the FA
content is increased from 60% to 75%, the specific heat is reduced
by 4% at 22 °C and 6% at 800 °C. As the PVA fiber content is
increased from 1.5% to 2.3%, the specific heat is reduced by 3% at
22 °C and 6% at 800 °C, likely due to the increase in porosity by
the addition of PVA fibers. The SP content appears to have less
effect on the specific heat.
Fig. 8. Specific heat vs. mix proportions.
 X. Li et al. / Construction and Building Materials 157 (2017) 829–838
4.4. Compressive strength and failure mode
As temperature increases, the difference in coefficients of ther-
mal expansion of matrix and aggregates causes internal stresses in
specimen. In addition, as temperature increases up to 200 °C, water
vaporization and AFt/AFm decomposition increase the porosity
and vapor pressure, causing microcracks in specimen. When the
temperature is no more than 200 °C, the vapor pressure is rela-
tively low and cracks are not substantially developed. On the other
hand, water vaporization leads to drying shrinkage, which tents to
reduce the porosity. Polymerization of the PVA fibers partially fills
the voids in the matrix [37]. Moreover, the high temperature steam
accelerates the hydration of unhydrated cement and pozzolanic
reaction of fly ash. Therefore, the compressive strength can be
slightly increased, as shown in Fig. 9(a). As the maximum temper-
ature is increased from 22 to 200 °C, the average compressive
strength is increased by 6%. After that, further increasing tempera-
ture reduces the compressive strength, due to the dehydration,
dehydroxylation, and decomposition of hydrates and the pyrolysis
of PVA fibers. The average compressive strength is reduced by 68%
after exposure to 800 °C. The compressive strength can be corre-
lated with the density, as plotted in Fig. 9(b). Overall, the compres-
sive strength increases with density at a rate of 174 MPa
cm3/g.
Fig. 10 shows the compressive strength associated with the mix
proportions. The compressive strength decreases with the w/b and
PVA fiber content, likely due to the fact that the porosity increases
with the w/b and PVA fiber content. As the w/b is increased from
0.24 to 0.36, the compressive strength is reduced by 24% at 22 °C
and 38% at 800 °C. As the PVA fiber content is increased from
1.5% to 2.3%, the compressive strength is reduced by 1% at 22 °C
and by 18% at 800 °C. Increasing s/b brings more ITZs, i.e. more
defects into the material, which tends to reduce the compressive
strength. As the s/b is increased from 0.36 to 0.66, the compressive
strength is reduced by 15% at 22 °C and by 21% at 800 °C.
80
Compressive strengtht (MPa)
60
40
20
0 0
0 200 400
(a) Temperature (°C)
Fig. 9. (a) Compressive strength (fc) vs. the heating temperature, error bars at 95% confident level. (b) Compressive strength vs. density.
Fig. 10. Compressive strength vs. mix proportions.
835
Increasing fly ash content leads to reduction in cement content,
hence, forming less cement hydrates during hydration. Since the
binding effect relies on the amount of hydrates, increasing the FA
content reduces the connectivity between particles. As the FA con-
tent is increased from 60% to 75%, the compressive strength is
reduced from by 8% at 22 °C. However, after the temperature is
beyond 400 °C, the compressive increases with the FA content,
revealing that the use of high-volume fly ash can improve the com-
pressive strength at high temperature, perhaps due to the poz-
zolanic reaction which lowers the CH content. As the FA content
is increased from 60% to 75%, the compressive strength is increased
by 16% at 800 °C. The SP content does not demonstrate significant
effect on the compressive strength.
The compressive failure mode also changes with temperature,
as shown in Fig. 11. No significant change in failure mode is
observed up to 200 °C. However, after exposure to 400 °C or higher
temperatures, the specimens become more susceptible to localized
failure such as corner cracks and surface flaking, demonstrating
deteriorated structural integrity in compression.
4.5. Tensile strength and ductility
The tensile strength decreases at elevated temperatures, as
shown in Fig.12(a). After exposure to 800 °C for 2 h, the specimens
were broken at installation for tensile test. Therefore, the tensile
strength for 800 °C was not tested. Different from the compressive
strength, as the maximum heating temperature is increased up to
200 °C, the average tensile is reduced by about 8%. As temperature
is increased up to 600 °C, the average tensile strength is reduced by
around 56%. The tensile strength can be correlated with the den-
sity, as plotted in Fig. 12(b). Overall, the tensile strength increases
with density at a rate of 10 MPa cm3/g.
Fig. 13 shows the tensile strength associated with the mix pro-
portions. As the w/b is increased from 0.24 to 0.36, the tensile
80
Compressive strength (MPa)
60
40
fc = 174 - 254
20 R² = 0.74
600 800 1.5 1.6 1.7 1.8 1.9 2
(b) Density (g/cm3)
836 X. Li et al. / Construction and Building Materials 157 (2017) 829–838

Ductility (%)
2

0
0 200 400 600 800
Temperature (°C)
Fig. 14. Tensile ductility (d) vs. the highest temperature, error bars at 95% confident
level.

is increased by 18% at 22 °C. However, after exposure to 400 °C,

Fig. 11. Failure modes of cube specimens in compressive test.
strength is reduced by 21% at 22 °C and 42% at 600 °C. As the s/b is
increased from 0.36 to 0.66, the tensile strength is decreased by
12% at 22 °C and 37% at 600 °C. As the FA content is increased from
60% to 75%, the tensile strength is reduced by 18% at 22 °C and
increased by 15% at 600 °C. The tensile strength increases with
the PVA fiber content at temperatures up to 200 °C. As the PVA
fiber content is increased from 1.5% to 2.3%, the tensile strength
the PVA fibers disappear and leave voids in matrix. Further increas-
ing the fiber content reduces the tensile strength. As the PVA fiber
content is increased from 1.5% to 2.3%, the tensile strength is
reduced by 38% at 600 °C. The SP content has negligible effect on
the tensile strength.
Before exposure to elevated temperatures, at onset of a crack in
a specimen, the randomly distributed PVA fibers crossing the crack
can bridge the crack and enables the specimen to carry higher
loads. With the increase in the load, the fibers can transfer the load
away from the crack faces, developing more cracks and enhancing
the ductility (i.e. ultimate strain) [18,19]. After exposure to ele-
vated temperatures, the PVA fibers are degraded, resulting in
reduction in ductility [24], as shown in Fig. 14. After exposure to
200 °C for 2 h, the average ductility of all mixtures is reduced by
76%. After the temperature increases to 400 °C, the specimens

5 5
Tenile strength (MPa)
Tensile strengtht (MPa)

4 4

3 3

2 2 ft = 10 - 14
R² = 0.74
1 1

0 0
0 200 400 600 800 1.5 1.6 1.7 1.8 1.9 2
(a) Temperature (°C) (b) Density (g/cm3)

Fig. 12. (a) Tensile strength (ft) vs. heating temperature, error bars at 95% confident level. (b) Tensile strength vs. density.

Fig. 13. Tensile strength vs. mix proportions.

 X. Li et al. / Construction and Building Materials 157 (2017) 829–838
Fig. 15. Tensile ductility vs. mix proportions.
become brittle due to the absence of PVA fibers. Changes in the
stress-strain curves were reported in [24].
Fig. 15 shows the results of tensile ductility associated with mix
proportions. The ductility decreases with the w/b and s/b, likely
due to the bond between PVA fibers and matrix, which decreases
with the w/b and s/b. As the w/b is increased from 0.24 to 0.36,
the ductility is reduced from 3.3% to 2.7% (by 18%) at 22 °C and
from 1.1% to 0.8% (by 26%) at 200 °C. As the s/b is increased from
0.36 to 0.66, the ductility is reduced from 3.3% to 2.7% (by 20%)
at 22 °C, and from 1.1% to 0.8% (by 26%) at 200 °C. As the fly ash
content is increased from 60% to 75%, the tensile ductility is
increased by 10% at 22 °C and 30% at 200 °C, possibly due to the
modification of interfacial bond between the PVA fiber and matrix.
The ductility increases with the PVA fiber content, likely due to the
enhanced bridging effect for cracks. As the PVA fiber content is
increased from 1.5% to 2.3%, the ductility is increased by about
20% at 22 °C and 40% at 200 °C. As the SP content is increased from
0.10% to 0.25%, the ductility is increased by about 15% at 22 °C and
35% at 200 °C, which can be attributed to the improved homogene-
ity due to the use of SP.
5. Conclusions
Based on the above research, conclusions are summarized as
follows.
 As the heating temperature increases from 22 to 800 °C, the
average thermal conductivity is reduced by 42%. Within the
investigated ranges, the thermal conductivity decreases with
the w/b and fiber content, and increases with the s/b and SP
content. The fly ash content appears to have limited effect on
the thermal conductivity.
 As the heating temperature increases from 22 to 800 °C, the
average volumetric specific heat is reduced by 19%. Within
the investigated ranges, the specific heat achieves the maxi-
mum values between the w/b from 0.24 to 0.36. The specific
heat decreases with the s/b at 22 °C, but increases with the
s/b from 400 to 600 °C. The specific heat marginally decreases
with the PVA fiber content. The FA and the SP contents appear
to have relatively small effects on the specific heat.
 As the heating temperature increases from 22 to 200 °C, the
average compressive strength is increased by 6%. Increasing
the maximum heating temperature from 200 to 800 °C reduces
the average compressive strength by 68%. The compressive
strength decreases with the w/b, the s/b, and the PVA fiber con-
tent. Increasing the FA content reduces the compressive
strength at 22 °C. However, as the maximum temperature goes
beyond 400 °C, the compressive increases with the FA content,
837
revealing that the use of high-volume fly ash can improve the
high temperature strength. The SP content does not demon-
strate significant effect on the compressive strength.
 As the heating temperature increases from 22 to 200 °C, the
average tensile strength is reduced by 8%. As temperature is
increased up to 600 °C, the average tensile strength is reduced
by 56%. The tensile strength decreases with the w/b and the
s/b. Increases in the FA content slightly reduce the tensile
strength at 22 °C. At 600 °C the tensile strength increases with
the FA content, revealing that the use of high-volume fly ash
can improve the high temperature tensile strength. The tensile
strength increases with the PVA fiber content at 22 and 200 °C,
while it decreases with the PVA fiber content at 400 and 600 °C.
The SP content does not demonstrate significant effect on the
tensile strength.
 The average tensile ductility of all mixtures is reduced by 68%
after exposure to 200 °C. After the heating temperature is
increased to 400 °C, the specimens become brittle. The tensile
ductility decreases with the w/b and the s/b, and it increases
with the PVA fiber, FA content, and the SP contents.
Acknowledgement
This study was funded by the Natural Science Foundation of
China [grant numbers 51278290 and 51108253]; the Project of
Shandong Province Higher Educational Science and Technology
Program [grant number J11LE09]; the Program of Changjiang
Scholars and Innovative Research Team [grant number
IRT13075]. The first author was funded by the China Scholarship
Council [grant number 201409995014] to visit Missouri University
of Science and Technology for one year.
References
[1] V. Kodur, A. Agrawal, An approach for evaluating residual capacity of
reinforced concrete beams exposed to fire, Eng. Struct. 110 (2016) 293–306.
[2] Y. Chen, F. Tang, Y. Bao, Y. Tang, G. Chen, A Fe-C coated long period fiber grating
sensor for corrosion induced mass loss measurement, Opt. Lett. 41 (10) (2016)
2306–2309.
[3] M. Ozel, Thermal performance and optimum insulation thickness of building
walls with different structure materials, Appl. Therm. Eng. 31 (17–18) (2011)
3854–3863.
[4] F. Tang, Y. Bao, Y. Chen, Y. Tang, G. Chen, Impact and corrosion resistances of
duplex epoxy/enamel coated plates, Constr. Build. Mater. 112 (2016) 7–18.
[5] W. Meng, K.H. Khayat, Experimental and numerical studies on flexural
behavior of ultra-high performance concrete panels reinforced with
embedded glass fiber-reinforced polymer grids, J. Transp. Res. Board 2592
(2016) 38–44.
[6] W. Meng, K.H. Khayat, Improving flexural behavior of ultra-high performance
concrete by rheology control, Comp. B Eng. 117 (2017) 26–34.
838 X. Li et al. / Construction and Building Materials 157 (2017) 829–838
[7] W. Meng, K.H. Khayat, Mechanical properties of ultra-high-performance
concrete enhanced with graphite nanoplatelets and carbon nanofibers,
Comp. B Eng. 107 (2016) 113–122.
[8] W. Meng, K.H. Khayat, Effect of hybrid fibers on fresh, mechanical properties,
and autogenous shrinkage of cost-effective UHPC, J. Mater. Civ. Eng. (2017),
https://doi.org/10.1061/(ASCE)MT.1943-5533.0002212. In Press.
[9] W. Meng, M. Valipour, K.H. Khayat, Optimization and performance of cost-
effective ultra-high performance concrete, Mater. Struct. 50 (1) (2017) 29p.
[10] Y. Bao, W. Meng, Y. Chen, G. Chen, K.H. Khayat, Measuring mortar shrinkage
and cracking by pulse pre-pump Brillouin optical time domain analysis with a
single optical fiber, Mater. Lett. 145 (2015) 344–346.
[11] W. Meng, K.H. Khayat, Effects of saturated lightweight sand content on key
characteristics of ultra-high-performance concrete, Cem. Concr. Res. (2017),
https://doi.org/10.1016/j.cemconres.2017.08.018.
[12] W. Meng, V.A. Samaranayake, K.H. Khayat, Factorial design and optimization of
UHPC with lightweight sand, ACI Mater. J. (2018), https://doi.org/10.14359/
51700995.
[13] Y. Bao, M. Valipour, W. Meng, K.H. Khayat, G. Chen, Distributed fiber optic
sensor-enhanced detection and prediction of shrinkage-induced delamination
of ultra-high-performance concrete bonded over an existing concrete
substrate, Smart Mater. Struct. 26 (2017) 085009, https://doi.org/10.1088/
1361-665X/aa71f4 (12pp).
[14] W. Meng. Design and performance of cost-effective ultra-high performance
concrete for prefabricated elements. PhD Dissertation, Missouri University of
Science and Technology, USA, 2017.
[15] W. Meng, K.H. Khayat. Flexural performance of ultra-high performance
concrete ballastless track slabs, in: Proceedings of 2016 Joint Rail
Conference, Columbia, South Carolina, United States, 2016. DOI:10.1115/
JRC2016-5814.
[16] W. Meng, K.H. Khayat. Development of stay-in-place formwork using GFRP
reinforced UHPC elements, in: Proceedings of 1st International Interactive
Symposium on UHPC, Des Moines, Iowa, United States, 2016.
[17] G. Peng, W. Yang, J. Zhao, Y. Liu, S. Bian, L. Zhao, Explosive spalling and residual
mechanical properties of fiber-toughened high-performance concrete
subjected to high temperatures, Cem. Concr. Res. 36 (4) (2006) 723–727.
[18] V.C. Li, On engineered cementitious composites (ECC) – a review of the
material and its applications, J. Adv. Concr. Technol. 1 (3) (2003) 215–230.
[19] V.C. Li, S. Wang, C. Wu, Tensile strain-hardening behavior of polyvinyl alcohol-
engineered cementitious composite (PVA-ECC), ACI Mater. J. 98 (6) (2001)
483–492.
[20] M. Sßahmaran, M. Lachemi, V.C. Li, Assessing mechanical properties and
microstructure of fire-damaged engineered cementitious composites, ACI
Mater. J. 107 (3) (2010) 297–304.
[21] M. Sß ahmaran, E. Özbay, H.E. Yücel, M. Lachemi, V.C. Li, Effect of fly ash and PVA
fiber on microstructural damage and residual properties of engineered
cementitious composites exposed to high temperatures, J. Mater. Civ. Eng.
23 (12) (2011) 1735–1745.
[22] V. Mechtcherine, F. de Andrade Silva, S. Müller, P. Jun, R.D. Toledo Filho.
Coupled strain rate and temperature effects on the tensile behavior of strain-
hardening cement-based composites (SHCC) with PVA fibers, Cem. Concr. Res.
42 (11) (2012) 1417–1427.
[23] T.K. Erdem, Specimen size effect on the residual properties of engineered
cementitious composites subjected to high temperatures, Cement Concr.
Compos. 45 (2014) 1–8.
[24] P.S. Bhat, V. Chang, M. Li, Effect of elevated temperature on strain-hardening
engineered cementitious composites, Constr. Build. Mater. 69 (2014) 370–380.
[25] K. Yu, J. Dai, Z. Lu, C.K.Y. Leung, Mechanical properties of engineered
cementitious composites subjected to elevated temperatures, J. Mater. Civ.
Eng. 27 (10) (2015) 04014268.
[26] K. Yu, Z. Lu, J. Yu, Residual compressive properties of strain-hardening
cementitious composite with different curing ages exposed to high
temperature, Constr. Build. Mater. 98 (2015) 146–155.
[27] J. Yu, J. Lin, Z. Zhang, V.C. Li, Mechanical performance of ECC with high-volume
fly ash after sub-elevated temperatures, Constr. Build. Mater. 99 (2015) 82–89.
[28] X. Li, H. Zhang, G. Chen, Y. Bao. Thermal properties of green high-performance
fiber-reinforced cementitious composites subjected to high temperature, in:
Proceedings of 9th International Conference on Structures in Fire, Princeton
University, United States, 2016.
[29] X. Li, J. Wang, Y. Bao, G. Chen, Cyclic behavior of damaged reinforced concrete
columns repaired with high-performance fiber-reinforced cementitious
composite, Eng. Struct. 136 (2017) 26–35.
[30] X. Li, Y. Bao, N. Xue, G. Chen, Bond strength of steel bars embedded in high-
performance fiber-reinforced cementitious composite before and after
exposure to elevated temperatures, Fire Saf. J. 92 (2017) 98–106.
[31] Y. Bao, Y. Chen, H. Matthew, C. Smith, B. Matthew, G. Chen, Experimental
analysis of steel beams subjected to fire conditions enhanced by Brillouin
scattering based fiber optic sensor data, J. Struct. Eng. 143 (1) (2016)
04016143.
[32] Y. Bao, M.S. Hoehler, C.M. Smith, M. Bundy, G. Chen, Temperature
measurement and damage detection in concrete beams exposed to fire using
PPP-BOTDA based fiber optic sensors, Smart Mater. Struct. 26 (8) (2017)
105034, https://doi.org/10.1088/1361-665X/aa89a9 (11pp).
[33] Y. Bao. Novel applications of pulse pre-pump Brillouin optical time domain
analysis for behavior evaluation of structures under thermal and mechanical
loading. PhD Dissertation, Missouri University of Science and Technology, USA,
2017.
[34] X. Huang, R. Ranade, Q. Zhang, W. Ni, V.C. Li, Mechanical and thermal
properties of green lightweight engineered cementitious composites, Constr.
Build. Mater. 48 (2013) 954–960.
[35] K.L. Scrivener, P. Juilland, P.J.M. Monteiro, Advances in understanding
hydration of Portland cement, Cem. Concr. Res. 78 (2015) 38–56.
[36] M.S. Magalhães, R.D. Toledo Filho, E.M.R. Fairbairn, Thermal stability of PVA
fiber strain hardening cement-based composites, Constr. Build. Mater. 94 (30)
(2015) 437–447.
[37] J. Shie, Y. Chen, C. Chang, J. Lin, D. Lee, C. Wu, Thermal pyrolysis of poly(vinyl
alcohol) and its major products, Energy Fuels 16 (2002) 109–118.
[38] W. Meng, P. Lunkad, A. Kumar, K.H. Khayat, Influence of silica fume and PCE
dispersant on hydration mechanisms of cement, J. Phys. Chem. C 120 (47)
(2016) 26814–26823.
[39] H. Tanyildizi, M. Sahin, Application of Taguchi method for optimization of
concrete strengthened with polymer after high temperature, Constr. Build.
Mater. 79 (2015) 97–103.
[40] GB/T 2419-2005. Test Method for Fluidity of Cement Mortar. Beijing, China,
2005.
[41] JGJ/T70-2009. Standard for Test Method of Performance on Building Mortar.
Beijing, China, 2009.
[42] C. Kittel, Introduction to Solid State Physics, John Wiley & Sons Inc, New York,
2005.
[43] M. Razeghi, Fundamentals of Solid State Engineering, Kluwer Academic
Publishers, New York, 2002.
[44] A. Qomi, M. Javad, F. Ulm, R.J.M. Pellenq, Physical origins of thermal properties
of cement paste, Phys. Rev. Appl. 3 (2015) 064010.
[45] E.S. Domalski, E.D. Hearing, Heat capacities and entropies of organic
compounds in the condensed phase. Volume III, J. Phys. Chem. Ref. Data 25
(1996) 1–525.